Low temperature vulcanization of monoolefin-nonconjugated polyolefin elastomeric interpolymers using hydroperoxides



3,407,158 LOW TEMPERATURE VULCANIZATION F MONOOLEFIN-NONCONJUGATED POLY- OLEFIN ELASTOMERIC INTERPOLYMERS USING HYDROPEROXIDES Agatino Guglielmino, Luigi Corbelli, and Enzo di Giulio, Ferrara, Italy, assignors to Montecatini Edison S.p.A., Milan, Italy No Drawing. Continuation-impart of application Ser. No. 450,522, Apr. 23, 1965.'This application Sept. 14, 1966, Ser. No. 579,215

Claimspriority, application Italy, Sept. 20, 1965, 20,898/ 65 26 Claims. (Cl. 260-235) ABSTRACT OF THE DISCLOSURE Vulcanization of ethylene/alpha-olefin/polyene terpolymer with organic hydroperoxide at a temperature below 60 C.

This application is a continuation-in-part of copending application Ser. No. 450,522, filed Apr. 23, 1965, now abandoned.

This invention relates to a process for cold vulcanization, with the aid of organic hydroperoxides, of high molecular weight, unsaturated, amorphous and substantially linear copolymers, consisting of at least two monomers selected from ethylene and higher alphaolelins and a monomer selected from cyclic or acyclic polyenes containing unconjugated double bonds.

More particularly, it relates to cold hydroperoxidic vulcanization of linear, amorphous and unsaturated ternited States Patent 0 f polymers of ethylene with propylene or butcne-l, and

linear cyclic or acyclic diolefins containing unconjugated double bonds, and to the vulcanizates obtained thereby.

It is known that in order to cure particular types of elastomeric saturated. polymers, particularly reactive agents, such as organic peroxides, possibly in the presence of free-radical acceptors, are required to be present.

Polymers of this nature, such as polyolefins, copolymers of ethylene with alpha-olefins, polyvinylalkylethers, silicone and polyurethane rubbers etc., require for their vulcanization the use of temperatures which are higher than 120 C., in order to allow a rapid decompositionof the peroxides into free radicals,

New types of copolymers having a low degree of unsaturation have recently been made available in the art, consisting of ethylene, an alpha-olefin and a third monomer selected from cyclic or acyclic polyenes having unconjugated double bonds, which copolymers are susceptible of being vulcanized with sulfur and conventional accelerants normally used for cross-linking unsaturated rubbers.

These new copolymers can also be hot vulcanized with the aid of organic peroxides by the methods heretofore used for vulcanizing saturated polymers, halogenated butyl rubber and various unsaturated rubbers.

.It. has now been found that the above mentioned newwe copolymers having alow degree of unsaturation can be cured with the aid of organic hydroperoxides, provided that the vulcanization is carried out at temperatures below 60 C. and that in the mix is present at least carbon black as reinforcing filler.

" Accordingly, the present invention provides a process for cold vulcanizing, that is at temperatures below 60 0, preferably between 5 and 60C., terpolymers derived from ethylene, a higher alpha-olefin, preferably, propylene or butene-l, andv a monomer selected from cyclic or acyclic polyenes having unconjugated double bonds with the aid of organic hydroperoxides as curing agents, and in the presence of carbon black.

3,407,158 Patented Oct. 22, 1968 ice The present invention also provides vulcanizable compositions comprising terpolymers of ethylene and a higher alpha-olefin, preferably propylene or butene-l, with a third monomer selected from cyclic and acyclic polyenes having unconjugated double bonds, a curing agent consisting of an organic hydroperoxide and, if desired, additives such as antioxidants, fillers other than carbon black and pigments.

The present invention is even more surprising since the curing, with the aid of hydroperoxides, of saturated polymers and butyl rubber, which, on the basis of their constitution are most similar to the terpolymers under consideration, gives insufficiently vulcanized polymers when carried out at the temperatures normally employed in peroxidic vulcanization (above C.), while at temperatures below 60 C. practically no vulcanization at all takes place.

The above results have been experimentally verified by vulcanization runs carried out on mixes based respectively on 100 parts of ethylene-propylene copolymer (ML (1+4) 100 0:35) and 100 parts of butyl rubber, each containing 50 parts of HAF carbon black and 5.7 parts of alpha-cumyl-hydroperoxide at a concentration of 70% in cumene, which, when vulcanized in a press at C. for 60 minutes, do not yield useful products (the mechanical characteristics cannot be determined), while at room temperature no vulcanization occurs, even after 60 days.

It is believed that the vulcanization rate of the terpolymers under consideration at a temperature in proximity to room temperature, using organic hydroperoxides, depends on the reactivity of the residual double bonds introduced, that is on the type of unconjugated double bond diolefinic cornonomer used in the terpolymerization.

In accordance with a preferred embodiment of the in vention, it has further been found that a cobalt or manganese salt of an aliphatic or cycloaliphatic longchained carboxylic acid, which salt is oil soluble, helps in raising the vulcanization rate at low temperature to an appreciable extent, when it is introduced into the mixes of a terpolymer of the said type containing an organic hydroperoxide as vulcanizing agent, and, optionally, sulfur and various additives and plasticizers.

In this Way, the vulcanization rate of the terpolymers can be increased and the curing time in some cases reduced from 12-20 days to 48-72 hours or less. By the use of suitable accelerators and selected temperatures, in fact, the vulcanization can be carried out also within times ranging from 2 to 48 hours.

The terpolymers of ethylene and higher alpha-olefins, with cyclic or acylic polymers having unconjugated double bonds, preferably comprise copolymers of ethylene, propylene or butene-l, and a third monomer selected from the group consisting of dicyclopentadiene, cyclooctadiene- 1,5, cyclooctadiene-1,4, cyclododecadiene-1,6, cyclododecadiene-1,7, cyclododecatriene-1,5,9, cycloheptadiene-l, 4, cyclohexadiene-1,4, norbornadiene, methylene-norbornene, 2-methylpentadiene-l,4, hexadiene-1,5, heptadiene-1,6, methyl-tetrahydroindene, hexadiene-1,4, etc.

The hydroperoxides usuable as vulcanizing agents in the present invention have the general formula ROOH wherein R is a tertiary aliphatic, cycloaliphatic or aromatic radical. Examples of suitable hydroperoxides include alpha-cumyl-hydroperoxide, p methane hydroperoxide, tert.-amyl-hydroperoxide, bromo tert.-bntyl hydroperoxide, m,p-di-isopropylbenzene-monohydroperoxide, m,pdi-isopropylbenzene-dihydroperoxide, etc.

The hydroperoxide curing agent may be introduced into the terpolymer mix in a calender, according to known methods, or can be sprayed in solution on the surface of the manufactured articles, depending on the intended applications for the vulcanizate.

The amount of hydroperoxide necessary to obtain vulcanizates having good mechanical characteristics varies considerably depending on the type of hydroperoxide used. In general, amounts of hydroperoxide ranging from about 0.01 to 20 parts by weight per 100 parts of terpolymer can be used.

The salts which can be used as accelerators in accordance with a preferred embodiment of the invention are cobalt or maganese salts of aliphatic or cycloaliphatic acids having 8 to 18 carbon atoms. Examples of such salts include the cobalt and maganese salts of n-octanoic acid, 2-ethyl-hexanoie acid, lauric acid, palmitic acid, stearic acid, linoleic acid and naphthenic acids. The amounts of accelerator used range from about 0.1 to 2 parts by weight per 100 parts of terpolymer.

The vulcanizable mixer, as usual in the art, can contain, in addition to the curing agent, and carbon black, also antioxidants, pigments, etc.

The presence of sulfur as coagent (which constitutes a further difference from peroxidic vulcanization of saturated olefin copolymers) does not seem to impart particular advantages. On the contrary, a degradation on the mechanical characteristics of the vlucanizates was occasionally observed.

The vulcanization temperatures are generally between about and 60 C. for a period of time ranging from 48 hours to days or even for a longer time. As already mentioned, when a vlucanization accelerator is used, shorter times of as little as two hours may sufiice.

As can be observed, due to the low temperatures adopted in the hydroperoxidic vulcanization, particularly long curing times are often required, but this is generally EXAMPLE '1 In a conventional type inner mixer, three different mixes comprising the following terpolymers were prepared at room temperature:

(1) Type PTerpolymer consisting of ethylene/ propylene (54% by mo1s)cyclooctadiene-l,5 (0.32 mol/kg.) ML (1+4) 100 0:49.

(2) Type QTerpolmer made up of ethylene/propylene (52% by mols)dicyclopentadiene (0.515 mol/kg.) ML (1+4) 100 (3.:30.

(3) Type RTerpolymer consisting of ethylene/propylene (49.5 mols )dicyclopentadiene (0.34 mol/ kg.)-ML (1+4) 100 C.=41.

Thick (0.8-0.9 mm.) laminae were prepared with mixes of the above terpolymers with carbon black and 70% by weight of alpha-cumyl hydroperoxide in cumene.

The vulcanization conditions, the composition of the terpolymer-based mixes and the mechanical characteristics of the vulcanizates in relationship with time are reported in Table 1.

TABLE 1 Mixes 1 2 3 Type P terpolymer, parts by weight 100 Type Q terpolymer, parts by weight 100 Type R terpolymer, parts by weight 100 HAF carbon black, parts by weight 50 50 50 Alpha-eumyl hydroperoxide (70%) in cumene, 5. 7 5.7 5. 7

parts by weight.

vulcanization temperature, C.

Time, days Tensile strength, kgJcm. 13 37 56 85 98 101 48 86 158 196 42 86 137 130 157 Elongation at break, percent 460 480 480 430 430 320 420 410 400 235 410 360 320 270 220 Elastic mod. at 200%, kg./em. 9 16 19 34 35 59 18 49 63 160 20 37 67 93 138 Elastic mod. at 300%, kg./cm. 11 23 31 58 62 96 32 68 112 32 69 126 Residual set at 100%, percent 52 39 34 29 28 25 28.5 16 11.5 7 27 205 13 10.5 8 5 not a disadvantage, since the range of this process com- EXAMPLE 2 prises vulcanization in situ of manufactured articles of Three mixes based on type p terpolymer of Example 1,

large dimensions and other articles which are heated with difficulty, and for which curing times have no particular importance. Further, when shorter curing times are required, the vulcanization accelerators of this invention may be employed.

The present invention finds its use e.g. in vulcanizing in situ sheets for tank lining, in the preparation of plugs to close holes in plastic sheets, as well as in all the usual applications such as manufacture of gaskets, tarpaulins,

containing carbon black and alpha-cumyl hydroperoxide (70%) in cumene in varying proportions were prepared at room temperature in a conventional type mixer, and lanilinae from 1.5 to 1.8 mm. thick were obtained therewit In Table 2 are reported the vulcanization conditions, the composition of the terpolymer-based mixes and the influence of varying amounts of alpha-cumyl-hydroperoxide (70%) in cumene on the mechanical characteristics and in general, articles produced on a small scale. 0 of the vulcanizates in relationship with time.

TABLE 2 Mixes 1 2 3 Type P terpolymer parts by weight 100 HAF carbon blackfparts by weight 50 28 23 Alpha-cumyl hydroperoxide (70%) in cumene, parts by weight. 2. 5. 7 10 vulcanization temperature, C.

Time, days 6 8 15 2 3 5 2 3 5 Tensile strength, kgJcm. 17 71 48 86 158 66 98 108 Elongation at break, percent.- 190 290 420 410 400 480 430 300 Elastic mod. at 200%, kg./crn. 1 43 18 40 63 20 40 81 Elastic mod. at 300% kgJCm. 1 32 (i8 112 38 72 108 Residual set (at 0), percent 50 18 28. 5 16 11.5 26 18 10 l Nouvulcanlzed.

EXAMPLE 3 Various mixes based on Q-type terpolymer of Example 1, containing carbon black, alpha-cumyl hydroperoxide and varying amounts of sulfur, were prepared in a mixer TABLE 4 Mixes 1 2 3 Type P terpolymer, parts by weight 100 100 100 Type Q, terpolymer, parts by weight. 100 100 100 Type R terpolymer, parts by weight. 100 100 100 HAF carbon-black, parts by weight" 50 50 50 50 50 50 50 50 50 Sulphur, parts by weight .42 0.84 0.42 0.84 0.42 0.84 Alpha-fiumyl hydroporoxide, 70% in cumene, parts by 5.7 5.7 5.7 5.7 5.7 5.7 5.7 5.7 5.7

weig

vulcanization temperature, C.

Time, hours Tensile strength, kgJcm. 43 22 18 121 66 50 98 91 67 Elongation at break, percent 430 450 400 250 305 315 315 380 400 Elastic mod. at 200%, kg./em. 21 14 14 96 42 35 48 36 29 Elastic mod. at 300%. kg./em. 33 17 17 61 48 92 69 52 Residual set at 100%, percent 40 45 41 14 24.5 44.5 26

at room temperature, with which mixes laminae from 0.8 35 i to 0.9 mm. thick were manufactured.

Table 3 shows the composition of the mixes, the curlng EXAMPLE 5 conditions and the mechanical characteristics of sulfurcontaining vulcanizates as compared with the ones obtained from a sulfur-free mix.

TABLE 3 Mixes 1 2 3 Type Q terpolymer parts by weight 100 100 100 HAF carbon black, parts by weight.-.. so so so Sulphur, parts by weight 0.4 0.84 Alpha-eumyl hydroperoxide 5. 7 5. 7 5. 7

(70%) in eumene, parts by weight.

vulcanization Temperature, C

Time, days Tensile strength, kgJemfl. 86 158 84 152 86 156 Elongation at break, percen 410 400 440 430 460 440 Elastic mod. at 200%, kgJcm 49 63 60 36 55 Elastic mod. at 300%, kgJcm 68 112 59 104 49 96 Residual set at 100, percent... 16 11.5 22 13 26 15. 5

EXAMPLE 4 In a common type mixer, three mixes based on terpolymers of type P and Q of Example 1, comprising alphacumyl-hydroperoxide, carbon black and varying amounts of sulfur, were prepared and laminae 1 mm. thick were obtained therefrom.

Then after vulcanization in an oven for 16 hours at 70 C. in a nitrogen stream, specimens of the laminae were taken for the determination of the mechanical characteristics.

The composition of the mixes, the vulcanization conditions and the mechanical characteristics of the vulcanizates in relation to the varying amounts of sulfur are shown in Table 5.

These characteristics show that vulcanization temperature above about 60 C. do not give satisfactory results. This example is therefore shown only for comparison.

TABLE 5 Mixes 1 2 Type P terpolymer, parts by weight 100 100 Type Q terpolymer, parts by weight 100 100 100 HAF carbon black, parts by weight 50 50 50 50 50 50 Sulphur, parts by weight 0.42 0.84 0. 42 0. 84 Alpha-cumyl-hydroperoxide, 70% in 5. 7 5. 7 5. 7 5. 7 5. 7 5. 7

eumene, parts by weigh t.

vulcanization temperature, C.

7 EXAMPLE 6 In a conventional type mixer, mixes based on terpolymers of type P and Q of Example 1 were prepared, com- Table 7 shows the composition of the mixes, the vulcanization conditions and the mechanical characteristics of the vulcanizates in relation to time.

TABLE 7 Mixes 1 Type Q terpolymer, parts by weight HAF carbon black, parts by weight p-Menthane-hydroperoxido (100%) parts by weight.

vulcanization temperature, C.

prising alpha-cumyl hydroperoxide (70% in cumene),

carbon black and varying amounts of sulfur, with which mixes laminae 1.25-1.50 mm. thick were manufactured and then vulcanized for 60 minutes at 150 C.

Table 6 reports the compositions of the mixes, the curing conditions and the mechanical characteristics of the vulcanizates in relation to the varying amounts of sulfur In a conventional inner mixer, two difierent mixes comprising the following terpolymers were prepared at room temperature:

- (1) M Type-Terpolymers consisting of ethylene/pro pylene by mols)/methyl-tetrahydroindene as compared with the vulcanizates of sulfur-free mixes. (0.395 mols/kg.) having a ML (1+4) at 100 The values of the characteristics, shown here for com- C.=64. parison only, show that the temperature normally used (2) N Type-Terpolymer consisting of ethylene/profor the curing with peroxides of the saturated ethylenepylene (31% by mols)/methylene-norbornene propylene copolymer, do not bring about useful results 30 (0.292 mols/kg.) having a ML (1+4) at 100 here. C.=91.

TABLE 8 Mixes 1 2 Type M terpolymer, parts by weight- Type N terpolymer, parts by weight- HAF carbon black, parts by weight- 70% alpha-eumyl-hydro-peroxide in cume parts by weight.

Tensile strength, kg./on1. Elongation at break, percent Elastic modulus at; 200%, kg.

Elastic modulus at 300%, kg./em. Residual set (100%), pcrcent 1 Broken.

TABLE 6 Mixes 1 2 Type I terpolymer, parts by weight.. 100 100 100 Type Q terpolymer, parts by weight 100 100 HAF carbon-black, parts by weight 50 Sulphur, parts by weight 0. 42 0. 84 0. 42 0. 84 Alpha-cumyl hydroperoxide, 70% in 5. 7 5. 7 5. 7 5. 7 5. 7 5. 7

cumene, parts by weight.

vulcanization temperature, C.

Time, minutes Tensile strength, kg./cm. 10 10 10 9 9 Elongation at break, perce 110 200 200 90 90 S0 Elastic mod. at 200%, kg./cm 10 Elastic mod. at 300%, kg./cm Residual set at 100%, percent 1 Broken.

EXAMPLE 7 A mix based on type Q terpolymer of Example 1 containing carbon black and 100% p-menthane hydroperoxide was prepared in a conventional type mixer. Laminae 1 mm. thick were manufactured from the mix and exposed to air at room temperature to supply specimens for the evaluation of the mechanical characteristics of the vulcanizates.

These mixes also contained carbon black and 70% alphacumyl hydroperoxide in cumene and were used to prepare 0.4 to 0.6 mm. thick sheets.

The vulcanization conditions, the composition of the terpolymer-based mixes and the mechanical characteristics of the vulcanizates are shown in Table 8 as a function of time.

EXAMPLE 9 In a conventional inner mixer three different mixes based on the following terpolymers were prepared at room temperature:

(1) Q TypeTerpolymer ethylene/propylene (52% by mols)/dicyclopentadiene (0.515 mol/kg.) having :1 ML (1+4) at C.=30.

(2) M TypeTerpolymer ethylene/propylene (40% by mols)/methyl-tetrahydroindene (0.395 moi/kg.) having a ML (1+4) at 100 C.=64.

From these mixes, containing also carbon black and diisopropylbenzene-dihydroperoxide, 0.5 to 0.7 mm. thick sheets were prepared.

The vulcanization conditions, the composition of the terpolymer-based mixes and the mechanical characteristics of the vulcanizates are shown in Table 9 as a function of time.

TABLE 9 Composition of the Mix 1 2 3 Type Q terpolymer, parts by weight 100 Type M terpolymer, parts by weight- 100 100 HAF carbon black, parts by weight 50 50 50 m-p-Diisopropylbenzene mono and dihydroperoxide in m-p-diisopropylbenzene (56% expressed as monohydroperoxide), parts by weight. 9. 1 9. 1 p-Diisopropylbenzene-dihydroperoinde, parts by we1ght 5. 95

vulcanization temperature 0. D 20 20 20 L Time, days Tensile strength, kg./err1. 88 125 169 164 179 166 32 50 61 85 96 105 86 94 105 107 122 114 Elongation at break, percent 360 360 360 340 350 290 385 390 365 360 400 395 350 325 310 245 250 210 Elasticmodulus at 200%, kg./cm. I 44 5s 84 88 01 s 27 30 44 44 50 40 4e 59 83 95 112 Elasticmodulus ata00%,k ./cm. 75 103 137- 146 150 27 41 52 74 74 81 71 80 102 Residual set at 100%, percent 24 16 15.5 12 11 9 34 26 20' 20 16.5 21 18.5 17.5 13.5 11 10 EXAMPLE 11 20 Three mixes of the following composition were pre- EXAMPLE 10 pared in a conventional mixer at room temperature.

In a conventional inner mixer at room temperature Ethylene/propylene (39% by there were prepared four diiferent mixes based on the ter- Qf g? Parts by polymers Q and M of Example 8. These mixes also con- 25 tained carbon black and diisopropylbenzene-dihydroper- 1 2 3 oxide and from these mixes 0.5 to 0.7 mm. thick sheets (0.1%gZr1ols1igJterpolymer ML (1+4) were prepared. The sheets were then vulcanized in an HAF carbon black 2g oven at 50 C. for 24 hours under a nitrogen current, and Alpha-eumyl-hydroperoxide (70% in specimens were prepared therefrom for the determination gf ffi (acceletatonuuu of the mechanical characteristics. 00 naphthenatc (accelerator) In Table 10 are shown the compositions of the mixes, the vulcanization conditions and the mechanical charac- From these miXeS, thick Specimens Were teristics f th l i t prepared and kept at room temperature (25 C.) for the times indicated in Table 11. Their mechanical characteristics were observed periodically as a function of time. The results are reported in Table 11.

TABLE 11 Mix Number Accelerator type amount (pp. by wt.) Co 2-eth361-g1exan0ate Co 2-ethyl1hexanoate (lo-naplhghenate Tensile Elong. at Elast. Set at Tensile Elong. at Tensile Elong. at

strength, break, Mod. at at 100%, strength, break, E200, Set, strength, break, E200, Set, kg./c1 11. percent k20;)%, percent kg./cm. percent kg./cm. percent kg./cm. percent kgJcm. percent 131 330 03 14 172 335 88 12 128 415 140 300 87 14 147 250 10s 12 Not determined N at determined Not determined 172 850 75 14 145 245 109 14 137 210 127 12 1 Not determined 130 230 114 12 141 220 134 12. 5 169 275 107 11 Not determined Not determined 1 152 245 111 10.5 143 200 143 10 115 205 112 12. 5 130 215 216 10. 5 128 200 128 Broken 99 180 Broken 95 170 Broken TABLE 10 Composition Of the M 1 2 3 I 4 Type Q terpolymer parts by weig 100 yp rpo y parts by welght 100 Mixes havmg the following composltlon were pre- HAF carbon black, parts by we1ght 50 50 50 d l m-p-Diisobeuzene 11101110 and 0111 9.1 9.1 pare In a conventiona mixer.

dro eroxide inm-piisopropy enzene (56 eXpreSSed as mono-hydroperoxide), Parts by weight parts by weight. M dr 5 95 2 97 Ethylene/propylene (35% by mols) /5 methyl- -D" enzene- 1 0 eroxi e 1 p grg iw Y D 1 tetrahydromdene (0.246 mols/kg.) terpolymer v ML (1+4) 100 C.==84 100 Vuleamzatwn temperature (in oven under a nitrogen HAF Carl a k 50 current) Alpha-cumyl-hydroperoxide in cumene) 5.7 50 50 50 50 Accelerators (various types) Variable & From these mixes 0.4-0.6 mm. thick specimens were 24 24 24 24 prepared and maintained at room temperature for the Tensile strength,kg./cm. 174 04 so 45 times indicated. Table 12 shows the values of the Elon ation at break, percent 305 280 250 00 Elastgic modulus at 200%,kgJcmL 98 44 58 27 chanical charactenst cs as a funct1on of time, compared Elastic modulus ata00%,kg./cm. 157 8 with the values obtained from mixes which do not con- Residual set at 100%, percent 12 26 15. 5

tain a vulcanization accelerator.

TABLE MiX number 1 2 Temperature, C 60 25 Time (hours) 2 4 Tensile strength (kg/cm!) 176 118 Elongation at break (percent)- 310 305 Elastic modulus at 200% (kg/cm?) 80 52 Elastic modulus at 300% (kg/cm?) 172 116 Deformation set at 100% (percent) 10 Without the accelerator, no vulcanization took place at the above times and temperatures.

While the present invention has been described with respect to specific examples, it is to be understood that these examples are for purposes of illustration, and that the invention is not limited thereto, since many variations and modifications can be practiced without departing from its spirit and scope.

Having thus described our invention, what we desire to secure by Letters Patent and hereby claim is:

1. A vulcanizable composition comprising an amorphous olefin terpolymer having a low degree of unsaturation, said terpolymer consisting of (1) ethylene, (2) a member selected from the group consisting of propylene and butene-l, and (3) a member selected from the group consisting of cyclic and acyclic polyenes containing unconjugated double bonds, carbon black as a reinforcing filler, and, as curing agent, an organic hydroperoxide of the general formula ROOH wherein R is selected from the group consisting of tertiary aliphatic, cycloaliphatic and aromatic radicals.

2. The composition of claim 1 wherein the organic hydroperoxide is present in amounts ranging from 0.01 to parts by weight per 100 parts of terpolymer.

3. The composition of claim 1 wherein said polyene having unconjugated double bonds is selected from the group consisting of dicyclopentadiene, cyclooctadiene- 1,5, cyclooctadiene 1,4, cyclododecadiene 1,6, cyclododecadiene 1,7, cyclododecatriene 1,5,9, cycloheptadiene 1,4, cyelohexadiene 1,4, norbornadiene, methylenenorbornene, 2 methyl-pentadiene 1,4, hexadiene- 1,5, heptadiene 1,6, 5 methyl-tetrahydroindene, and hexadiene-1,4.

4. The composition of claim 2 wherein said polyene having unconjugated double bonds is selected from the group consisting of dicyclopentadiene, cyclooctadiene-1,5, cyclooctadiene 1,4, cyclododecadiene 1,6, cyclododecadiene 1,7, cyclododecatriene 1,5,9, cycloheptadiene 1,4, cyclohexadiene 1,4, norbornadiene, methylenenorbornene, 2 methyl-pentadiene 1,4, hexadiene 1,5, heptadienc 1,6, 5 methyl-tetrahydroindene, and hcxadiene- 1,4.

5. The composition of claim 1 wherein the organic hydroperoxide is selected from the group consisting of alpha-cumyl hydroperoxide, p-menthane-hydroperoxide, tert.amyl hydroperoxide, bromo tert.butyl hydroperoxide, m,p di isopropylbenzene monohydroperoxide, and m,p di isopropylbenzene dihydroperoxide.

6. The composition of claim 4 wherein the organic hydroperoxide is selected from the group consisting of alpha-cumyl hydroperoxide, p-menthane-hydroperoxide, tert.amyl hydroperoxide, bromo tertbutyl hydroperoxide, m,p-di-isopropyl-benzene monohydroperoxide, and m,p di isopropylbenzene dihydroperoxide.

7. The composition of claim 1 wherein the low unsaturation terpolymer contains 20-80% by mols of ethylene and 0.1 to 18% by mols of polyene, the remainder consisting of propylene or butene-l.

8. The composition of claim 6 wherein the low unsaturation terpolymer contains 20-80% by mols of ethylene and 0.1 to 18% by mols of polyene, the remainder consisting of propylene 0r butene-l.

9. The composition of claim 8 wherein said terpolymer has a molecular weight between about 20,000 and 800,000.

10. The composition of claim 9 wherein said molecular weight is between about 60,000 and 500,000.

11. The composition of claim 1 which further includes from about 0.1 to 2 parts by weight per parts of terpolymer of a vulcanization accelerator selected from the group consisting of the cobalt and manganese salts of aliphatic and cycloaliphatic carboxylic acids containing 8-18 carbon atoms.

12. The composition of claim 10 which further includes from about 0.1 to 2 parts by weight per 100 parts of terpolymer of a vulcanization accelerator selected from the group consisting of the cobalt and manganese salts of aliphatic and cycloaliphatic carboxylic acids containing 8-18 carbon atoms.

13. The composition of claim 11 wherein said aliphatic and cycloaliphatic carboxylic acids are selected from the group consisting of n-octanoic, Z-ethyl-hexanoic, lauric, palmitic, stearic, linoleic acid and naphthenic acids.

14. The composition of claim 12 wherein said aliphatic and cycloaliphatic carboxylic acids are selected from the group consisting of n-octanoic, 2-ethyl-hexanoic, lauric, palmitic, stearic, linoleic acid and naphthenic acids.

15. A process for vulcanizing an amorphous olefin terpolymer having a low degree of unsaturation, said process comprising heating a homogeneous mix consisting of the composition of claim 1 at a temperature below 60 C.

16. A process for vulcanizing an amorphous olefin terpolymer having a low degree of unsaturation, said process comprising heating a homogeneous mix consisting of the composition of claim 10 at a temperature below 60 C.

17. A process for vulcanizing an amorphous olefin terpolymer having a low degree of unsaturation, said process comprising heating a homogeneous mix consisting of the composition of claim 11 at a temperature below 60 C.

18. A process for vulcanizing an amorphous olefin terpolymer having a low degree of unsaturation, said process comprising heating a homogeneous mix consisting of the composition of claim 14 at a temperature below 60 C.

19. The process of claim 15 wherein the heating takes place at a temperature of from 5 to 60 C.

20. The process of claim 17 wherein the heating takes place at a temperature of from 5 to 60 C.

21. The process of claim 18 wherein the heating takes place at a temperature of from 5 to 60 C.

22. The process of claim 16 wherein the vulcanization time is between about 48 hours and 15 days.

23. The process of claim 17 wherein the vulcanization time is between about 2 and 72 hours.

24. The process of claim 21 wherein the vulcanization time is between about 2 and 72 hours.

25. A vulcanizate obtained by the process of claim 15.

26. A vulcanizate obtained by the process of claim 17.

References Cited UNITED STATES PATENTS 3,000,867 9/1961 Fisher 260-882 3,310,523 3/1967 Lenas 260-41 3,325,442 6/1967 McManimie 260-41 OTHER REFERENCES Haxo, Jr., et al: A New Sulfur-Cura-ble-Ethylene- Propylene Rubber, Rubber Age, November 1963, pp. 255-258.

Noller et al.: Effect of Acceleratorsof Polyesters, Modern Plastics, August 1962, pp. 150, 152 and 154.

DONALD E. CZAIA, Primary Examiner.

R. A. WHITE, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,407,158 October 22, 1968 Agatino Guglielmino et al.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

In the heading to the printed specification, line 3, "MONOOLEFIN-NONCONJUGATED" should read MONOOLEFIN-NONaCON- JUGATED Column 1 line 70 "bonds with" should read bond: with Column 2, line 63, "methane" should read menthane Column 3, line 8, "maganese" should read manganese line 10, "maganese" should read manganese Columns 9 and 10, TABLE 9, about the middle of the table, "Vulcanization temperature c." should read Vulcanization temperature C. and to the right of this heading, cancel "P". Column 9,

TABLE 10, first column, line 4 thereof, "Diisobenzene" should read Diisopropylbenzene Signed and sealed this 3rd day of March 1970.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. I WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents 

